In this work, Co3O4 nanowire arrays are prepared in-situ on the flat alumina substrates via a simple hetero-epitaxial growth without adding seed layers. It is found that the density of Co3O4 nanowires can be regulated by varying the concentration of NH4F that acts as substrate activation promoting the formation of nuclei on alumina substrate. In order to improve the gas-sensing performance, porous NiO nanosheets are anchored on the surface of Co3O4 nanowire arrays to form a novel heterostructure (Co3O4/NiO). Gas-sensing tests indicate a higher response value of these array composites towards ethanol (Rg/Ra = 4.26) than that of pristine Co3O4 nanowire arrays (Rg/Ra = 1.27) and NiO nanosheets (Rg/Ra = 1.89). The improved gas-sensing performances resulting from the special array structures and novel heterojunctions can provide abundant diffusion channels for gas molecules as well as a synergistic effect between Co3O4 and NiO.